@article{Winter199914Ele-13933,
  year={1999},
  doi={10.1021/ja990621w},
  title={14-Electron Four-Coordinate Ru(II) Carbyl Complexes and their Five-Coordinate Precursors : Synthesis, Double Agostic Interactions, and Reactivity},
  number={35},
  volume={121},
  issn={0002-7863},
  journal={Journal of the American Chemical Society},
  pages={8087--8097},
  author={Winter, Rainer F. and Huang, Dejian and Streib, William E. and Bollinger, John C. and Caulton, Kenneth G. and Scheiring, Thomas},
  note={Publikation aus Zusammenarbeitsprojekten}
}

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    <dc:contributor>Scheiring, Thomas</dc:contributor>
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    <dc:contributor>Huang, Dejian</dc:contributor>
    <dcterms:bibliographicCitation>First publ. in: Journal of the American Chemical Society 121(1999), 35, pp. 8087–8097</dcterms:bibliographicCitation>
    <dc:contributor>Bollinger, John C.</dc:contributor>
    <dcterms:title>14-Electron Four-Coordinate Ru(II) Carbyl Complexes and their Five-Coordinate Precursors : Synthesis, Double Agostic Interactions, and Reactivity</dcterms:title>
    <dcterms:abstract xml:lang="eng">The structure of five-coordinate Ru(II) complexes RuHCl(CO)(PiPr3)2, 1, RuCl2(CO)(PiPr3)2, 2, and Ru(Ph)Cl(CO)(PtBu2Me)2, 12, are reported. All three of these complexes have square-based pyramid geometry with the strongest σ-donor ligand trans to the vacant site. These 16-electron complexes do not show bona fide agostic interactions. This is attributed to the strong trans influence ligand (H, CO, and Ph) and π-donation of the Cl, which is further supported by the fact that two agostic interactions are present in the Cl- removal product of 12, i.e., the four-coordinate [RuPh(CO)L2]BAr‘4 (L = PtBu2Me, Ar‘ = 3,5-C6H3(CF3)2), 16. Structural comparison of 16 and 12 reveals that removal of Cl- does not change the remaining ligand arrangements but creates two low-lying LUMOs for agostic interactions, which persist in solution as evidenced by IR spectroscopy. Reactions of 16 with E−H (E = B, C(sp)) bonds cleave the Ru−Ph bond and form Ru−E/H bonds by different mechanisms. The reaction with catecholborane gives [RuH(CO)L2]BAr‘4, which further reacts with catecholborane to give [Ru(BR2)(CO)L2]BAr‘4. However, the reaction with Me3SiCCH undergoes a multistep transformation to give a PhCCSiMe3- and Me3SiCCH-coupled product, the mechanism of which is discussed. Reaction of RuCl2(CO)L2 with 1 equiv MeLi affords RuMeCl(CO)L2, 5, which further reacts with MeLi forming RuMe2(CO)L2, 7. Variable-temperature 13C{1H} NMR spectra reveal the two methyls in 7 are inequivalent and exchange by overcoming an energy barrier of 6.8 kcal/mol at −30 °C. The chloride of 5 can be removed to give [RuMe(CO)L2]BAr‘4.</dcterms:abstract>
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    <dc:creator>Caulton, Kenneth G.</dc:creator>
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    <dc:contributor>Winter, Rainer F.</dc:contributor>
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    <dc:contributor>Caulton, Kenneth G.</dc:contributor>
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    <dc:creator>Bollinger, John C.</dc:creator>
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